CN107936048A - A kind of preparation method of 2 fluorine, 4 methyl, 3 pyridine boronic acid - Google Patents
A kind of preparation method of 2 fluorine, 4 methyl, 3 pyridine boronic acid Download PDFInfo
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- CN107936048A CN107936048A CN201810043249.9A CN201810043249A CN107936048A CN 107936048 A CN107936048 A CN 107936048A CN 201810043249 A CN201810043249 A CN 201810043249A CN 107936048 A CN107936048 A CN 107936048A
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- methyl
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- pyridine boronic
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 title abstract description 8
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 title abstract 9
- 229910052731 fluorine Inorganic materials 0.000 title abstract 9
- 239000011737 fluorine Substances 0.000 title abstract 9
- ABMYEXAYWZJVOV-UHFFFAOYSA-N pyridin-3-ylboronic acid Chemical compound OB(O)C1=CC=CN=C1 ABMYEXAYWZJVOV-UHFFFAOYSA-N 0.000 title abstract 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- 235000011121 sodium hydroxide Nutrition 0.000 claims abstract description 9
- -1 3 pyridine boronic acid ester Chemical class 0.000 claims abstract description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 4
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000012043 crude product Substances 0.000 claims abstract description 3
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- 230000007062 hydrolysis Effects 0.000 claims abstract description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 3
- 238000006138 lithiation reaction Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 238000000605 extraction Methods 0.000 claims description 18
- LSZMVESSGLHDJE-UHFFFAOYSA-N 2-bromo-4-methylpyridine Chemical class CC1=CC=NC(Br)=C1 LSZMVESSGLHDJE-UHFFFAOYSA-N 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 12
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000013517 stratification Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 239000004327 boric acid Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 claims description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims 1
- 150000002240 furans Chemical class 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 abstract 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract 2
- 229910052794 bromium Inorganic materials 0.000 abstract 2
- 238000004519 manufacturing process Methods 0.000 abstract 2
- 238000012805 post-processing Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 6
- NOXNXVPLDITALF-UHFFFAOYSA-N butoxyboronic acid Chemical class CCCCOB(O)O NOXNXVPLDITALF-UHFFFAOYSA-N 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 239000000284 extract Substances 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
Abstract
The invention belongs to technical field of organic synthesis, more particularly to a kind of preparation method of 2 fluorine, 4 methyl, 3 pyridine boronic acid, the preparation method is using 2 fluorine, 3 bromine, 4 picoline as raw material, lithium halogen exchange reaction occurs with lithiation reagent and borating agent at low temperature for 2 fluorine, 3 bromine, 4 picoline and 2 fluorine, 4 methyl, 3 pyridine boronic acid ester is made by one kettle way in boronation reaction, obtained 2 fluorine, 4 methyl, 3 pyridine boronic acid ester 4 methyl of obtained 2 fluorine, 3 pyridine boronic acid crude product after the sodium hydrate aqueous solution hydrolysis of mass concentration 10%, it is finally purified to obtain 2 fluorine, 4 methyl, 3 pyridine boronic acid sterling, the reaction is used as reaction dissolvent by the use of tetrahydrofuran.The advantages of 2 fluorine, 4 methyl, 3 pyridine boronic acid preparation method of the invention, is cheap and easy to get using raw material, and reaction condition is gentle, and post-processing operation is simple, and production cost is relatively low, high income, reduces reaction cost, is adapted to industrialized production.
Description
Technical field：
The present invention relates to technical field of organic synthesis, and in particular to a kind of preparation side of the fluoro- 4- methyl -3- pyridine boronic acids of 2-
Method.
Background technology：
The character of the fluoro- 4- methyl -3- pyridine boronic acids of 2- is white solid powder, is in a kind of very extensive chemical industry of purposes
Mesosome, is widely used in medicine and the synthesis of other fine chemical products.
The content of the invention：
The technical problems to be solved by the invention are to provide the fluoro- 4- of 2- that a kind of purity is high, technique is simple and cost is low
The preparation method of methyl -3- pyridine boronic acids.
The technical problems to be solved by the invention are realized using following technical solution：
Using the bromo- 4- picolines of the fluoro- 3- of 2- as raw material, the bromo- 4- picolines of the fluoro- 3- of 2- at low temperature with lithiation reagent and
Lithium halogen exchange reaction occurs for borating agent and the fluoro- 4- methyl -3- pyridine boronic acid esters of 2- are made by one kettle way in boronation reaction, is made
The fluoro- 4- methyl -3- pyridine boronic acids esters of 2- with the fluoro- 4- first of 2- is made after the hydrolysis of the sodium hydrate aqueous solution of mass concentration 10%
Base -3- pyridine boronic acid crude products, finally purified to obtain the fluoro- 4- methyl -3- pyridine boronic acid sterlings of 2-, which is made with tetrahydrofuran
For reaction dissolvent.
A kind of preparation method of the fluoro- 4- methyl -3- pyridine boronic acids of 2-, it is characterised in that comprise the following steps：
(1) under nitrogen protection, first by the bromo- 4- picolines of the fluoro- 3- of 2- and butyl borate input reaction vessel, add
Tetrahydrofuran, cooling, is then added dropwise n-BuLi, mixing control dropping temperature is protected at -90~-50 DEG C after being added dropwise
Temperature reaction；
(2) the sodium hydrate aqueous solution stirring of mass concentration 10% is added into reaction system after reaction, will be reacted
The pH value of liquid is transferred to 13, then stratification, through extraction, merges water phase；
(3) water obtained is mutually extracted with methyl tertiary butyl ether(MTBE), and impurity extraction in water phase is come out, the water after extraction is mutually dropped
Concentrated hydrochloric acid is added dropwise to less than 0 DEG C in temperature, and the pH value of water phase is transferred to 2-3, separates out white solid, is filtered, obtain the fluoro- 4- methyl of 2--
3- pyridine boronic acid sterlings.
The molar ratio of the bromo- 4- picolines of the fluoro- 3- of 2- and n-BuLi is in the step (1)：1:(1.0-
1.5), preferably 1:1.2, the concentration of n-BuLi is 2.5mol/L.
The dropping temperature of n-BuLi is -90~-50 DEG C, preferably dropping temperature -80~-60 DEG C in the step (1)
Borating agent is triisopropyl borate ester in the step (1), butyl borate, trimethylborate, preferred boric acid three
Butyl ester.
The molar ratio of the bromo- 4- picolines of the fluoro- 3- of 2- and butyl borate is in the step (1)：1:(1.0-
2), preferably 1:1.5.
In order to make the technical means, the creative features, the aims and the efficiencies achieved by the present invention easy to understand, tie below
Specific embodiment is closed, the present invention is further explained.
Embodiment 1
(1) one kettle way prepares the fluoro- 4- methyl -3- pyridine boronic acids of 2-：Under condition of nitrogen gas protection, in 1000mL three-necked flasks
The bromo- 4- picolines of the fluoro- 3- of 60g2- are added, 109g butyl borates, tetrahydrofuran solvent, cools to -80 DEG C, be then added dropwise
N-BuLi 152ml, is added dropwise process and is kept for -80 DEG C, and insulation reaction is carried out after being added dropwise, and controlling reaction temperature is -80 DEG C, system
Obtain the fluoro- 4- methyl -3- pyridine boronic acid esters of 2-.
(2) purify：The sodium hydrate aqueous solution stirring of mass concentration 10% is added into reaction system after reaction, will
The pH value of reaction solution is transferred to 13, then stratification, through extraction, merges water phase.Obtained water mutually extracts 2 with methyl tertiary butyl ether(MTBE)
It is secondary, impurity extraction in water phase is come out, the water after extraction is mutually cooled to less than 0 DEG C, concentrated hydrochloric acid is added dropwise, by the pH value tune of water phase
To 2-3, white solid is separated out, filtering, obtains the fluoro- 4- methyl -3- pyridine boronic acids sterling 37.2g of 2-, yield 76%.
Embodiment 2
(1) one kettle way prepares the fluoro- 4- methyl -3- pyridine boronic acids of 2-：Under condition of nitrogen gas protection, in 1000mL three-necked flasks
The bromo- 4- picolines of the fluoro- 3- of 60g2-, 87g butyl borates are added, tetrahydrofuran solvent cools to -60 DEG C, is then added dropwise just
Butyl lithium 139ml, is added dropwise process and is kept for -60 DEG C, and insulation reaction is carried out after being added dropwise, and controlling reaction temperature is -60 DEG C, is made
The fluoro- 4- methyl -3- pyridine boronic acid esters of 2-.
(2) purify：The sodium hydrate aqueous solution stirring of mass concentration 10% is added into reaction system after reaction, will
The pH value of reaction solution is transferred to 13, then stratification, through extraction, merges water phase.Obtained water mutually extracts 2 with methyl tertiary butyl ether(MTBE)
It is secondary, impurity extraction in water phase is come out, the water after extraction is mutually cooled to less than 0 DEG C, concentrated hydrochloric acid is added dropwise, by the pH value tune of water phase
To 2-3, white solid is separated out, filtering, obtains the fluoro- 4- methyl -3- pyridine boronic acids sterling 28.4g of 2-, yield 58%.
Embodiment 3
(1) one kettle way prepares the fluoro- 4- methyl -3- pyridine boronic acids of 2-：Under condition of nitrogen gas protection, in 1000mL three-necked flasks
The bromo- 4- picolines of the fluoro- 3- of 60g2- are added, 109g butyl borates, tetrahydrofuran solvent, cools to -70 DEG C, be then added dropwise
N-BuLi 139ml, is added dropwise process and is kept for -70 DEG C, and insulation reaction is carried out after being added dropwise, and controlling reaction temperature is -70 DEG C, system
Obtain the fluoro- 4- methyl -3- pyridine boronic acid esters of 2-.
(2) purify：The sodium hydrate aqueous solution stirring of mass concentration 10% is added into reaction system after reaction, will
The pH value of reaction solution is transferred to 13, then stratification, through extraction, merges water phase.Obtained water mutually extracts 2 with methyl tertiary butyl ether(MTBE)
It is secondary, impurity extraction in water phase is come out, the water after extraction is mutually cooled to less than 0 DEG C, concentrated hydrochloric acid is added dropwise, by the pH value tune of water phase
To 2-3, white solid is separated out, filtering, obtains the fluoro- 4- methyl -3- pyridine boronic acids sterling 33.3g of 2-, yield 68%.
Embodiment 4
(1) one kettle way prepares the fluoro- 4- methyl -3- pyridine boronic acids of 2-：Under condition of nitrogen gas protection, in 1000mL three-necked flasks
The bromo- 4- picolines of the fluoro- 3- of 60g2- are added, 94.4g butyl borates, tetrahydrofuran solvent, cools to -80 DEG C, be then added dropwise
N-BuLi 126ml, is added dropwise process and is kept for -80 DEG C, and insulation reaction is carried out after being added dropwise, and controlling reaction temperature is -80 DEG C, system
Obtain the fluoro- 4- methyl -3- pyridine boronic acid esters of 2-.
(2) purify：The sodium hydrate aqueous solution stirring of mass concentration 10% is added into reaction system after reaction, will
The pH value of reaction solution is transferred to 13, then stratification, through extraction, merges water phase.Obtained water mutually extracts 2 with methyl tertiary butyl ether(MTBE)
It is secondary, impurity extraction in water phase is come out, the water after extraction is mutually cooled to less than 0 DEG C, concentrated hydrochloric acid is added dropwise, by the pH value tune of water phase
To 2-3, white solid is separated out, filtering, obtains the fluoro- 4- methyl -3- pyridine boronic acids sterling 31.8g of 2-, yield 65%.
The basic principles, main features and the advantages of the invention have been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (6)
- A kind of 1. preparation method of the fluoro- 4- methyl -3- pyridine boronic acids of 2-, it is characterised in that：The preparation method is bromo- with the fluoro- 3- of 2- 4- picolines are raw material, and the bromo- 4- picolines of the fluoro- 3- of 2- occur lithium halogen with lithiation reagent and borating agent at low temperature and exchange The fluoro- 4- methyl -3- pyridine boronic acid esters of 2-, the obtained fluoro- 4- methyl -3- pyridines of 2- is made by one kettle way in reaction and boronation reaction Borate after the sodium hydrate aqueous solution hydrolysis of mass concentration 10% with the fluoro- 4- methyl -3- pyridine boronic acid crude products of 2- are made, finally Purified to obtain the fluoro- 4- methyl -3- pyridine boronic acid sterlings of 2-, which is used as reaction dissolvent by the use of tetrahydrofuran。
- 2. a kind of preparation method of the fluoro- 4- methyl -3- pyridine boronic acids of 2-, it is characterised in that comprise the following steps：(1) under nitrogen protection, first by the bromo- 4- picolines of the fluoro- 3- of 2- and butyl borate input reaction vessel, tetrahydrochysene is added Furans, cooling, is then added dropwise n-BuLi, and mixing control dropping temperature carries out keeping the temperature anti-at -90~-50 DEG C after being added dropwise Should；(2) the sodium hydrate aqueous solution stirring of mass concentration 10% is added into reaction system after reaction, by reaction solution PH value is transferred to 13, then stratification, through extraction, merges water phase；(3) water obtained is mutually extracted with methyl tertiary butyl ether(MTBE), and impurity extraction in water phase is come out, the water after extraction is mutually cooled to Less than 0 DEG C, concentrated hydrochloric acid is added dropwise, the pH value of water phase is transferred to 2-3, separates out white solid, filtering, obtains the fluoro- 4- methyl -3- pyrroles of 2- Pyridine boric acid sterling.
- 3. the preparation method of the fluoro- 4- methyl -3- pyridine boronic acids of 2- according to claim 2, it is characterised in that：The 2- The molar ratio of the bromo- 4- picolines of fluoro- 3- and n-BuLi is：1:(1.0-1.5), preferably 1:1.2 n-BuLi is dense Spend for 2.5mol/L.
- 4. the preparation method of the fluoro- 4- methyl -3- pyridine boronic acids of 2- according to claim 2, it is characterised in that：The positive fourth The dropping temperature of base lithium is -90~-50 DEG C, preferably dropping temperature -80~-60 DEG C.
- 5. the preparation method of the fluoro- 4- methyl -3- pyridine boronic acids of 2- according to claim 2, it is characterised in that：The boronation Reagent is triisopropyl borate ester, butyl borate, trimethylborate, preferred boric acid tributyl.
- 6. the preparation method of the fluoro- 4- methyl -3- pyridine boronic acids of 2- according to claim 2, it is characterised in that：The 2- The molar ratio of the bromo- 4- picolines of fluoro- 3- and butyl borate is：1:(1.0-2), preferably 1:1.5.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112159421A (en) * | 2020-10-10 | 2021-01-01 | 珠海奥博凯生物医药技术有限公司 | Preparation method of 2-fluoro-4-methyl-3-pyridineboronic acid |
| CN112321622A (en) * | 2020-11-28 | 2021-02-05 | 沧州普瑞东方科技有限公司 | Preparation method of N-aryl carbazole-3-boric acid |
| CN113004312A (en) * | 2021-03-01 | 2021-06-22 | 陕西维世诺新材料有限公司 | Method for preparing 2-chloroquinoline-3-boric acid |
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| CN102627663A (en) * | 2012-03-23 | 2012-08-08 | 上海泰坦化学有限公司 | Preparation method of fluorine-containing pyridine boric acid |
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| CN112159421A (en) * | 2020-10-10 | 2021-01-01 | 珠海奥博凯生物医药技术有限公司 | Preparation method of 2-fluoro-4-methyl-3-pyridineboronic acid |
| CN112321622A (en) * | 2020-11-28 | 2021-02-05 | 沧州普瑞东方科技有限公司 | Preparation method of N-aryl carbazole-3-boric acid |
| CN113004312A (en) * | 2021-03-01 | 2021-06-22 | 陕西维世诺新材料有限公司 | Method for preparing 2-chloroquinoline-3-boric acid |
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Application publication date: 20180420 |